Vitamin recovery



Patented Dec. 9, 1947 are orrlca y 2. 212.131 VETAMIN REMWERY Walter Russell Trent, North Arlington, N. .L, as-

signor to Coiaatedalmoiive-Peet Company, Jersey City, N. J a corporation of Delaware No Drawing. Application August 11, 1944, Serial No. 549.129

8 Claims. (Cl. 167-81) 2 The present invention relates to the recovery In applicant's copending application. Serial No. of valuable constituents of animal and vegetable 462.370, filed October 1'7, 1942, methods are de oils and fats, and, in particular, to novel methods scribed whereby fatty materials, such as animal for the recovery of vitamins. sterols, and other and vegetable oils and fats, may be treated at constituents of fatty materials 5 low temperatures to convert the fatty glycerides Heretofore, in the recover of vitamins and present into fatty acid esters by reacting the other by-products from fatty materials such as fatty glycerides with an alcohol in the presence palm oil, cottonseed oil, menhaden oil, wool fat, of an alcoholysis catalyst. This reaction also is and the like. it has bee u ual practice to adapted for use in treating fatty materials, such L subject the material directly to extraction or as wool fat, for example, whereby complex or distillation treatment. However, such methods high molecular weight esters and compounds are require the treatment of large volumes of mateconverted into relatively low-boiling alkyl esters rial, and, when distillation is employed for sepaby reactions which may be carried out at room rating the by-products, the temperature and temperatures or with moderate heating.

length of time required for the separation are fre- In accordance with the present invention, such q y o h h n p l n d h t ce of the reaction products may be treated in various desirable s nt d pa t y t e aways to produce a relatively concentrated solution mills. y e destroyed o adversely affected, and containing the vitamins and other by-products, the products Obtained may be darkened in 00101 and this solution is treated to recover valuable In accordance with the present invention, fatty constituents therefrom. 1 materials containing constituents such as vita- In accordance with one method usedin treatmins, SteIOlS. lanolin, other Valuable ing the reaction products obtained by alcoholysis p n s, re first subjected to an alcoholysis reacof the fatt material. the reaction products are tion at relatively low temperatures and in the flash distilled directly to separate the unreacted presence of an alcoholysis catalyst, to convert the al h l, alkyl esters and glycerine produced, fa ty glycerides n mp x esters present into whereby a residue is left which contains the valp e alkyl ste s. These esters a e then puable by-products such as vitamins. In the alarated from the unreacted materials. Which 'i ternative, the alkyl esters of the fatty acids and clude the vitamins and other by-p od cts, W the glycerine produced by the alcoholysis reacby the latter constituents are concentrated into S, tion may be allcwed to eparate into layers where small volume of material which, in turn, may be i the upper layer contains the alkyl esters and treated at relatively low temperature and for a any unreacted glycerides, aswell as the unesterishort period of time to effect the separation or fl d a d unsaponified reaction roducts, includp lfication of the vitamins and other desired ing those vitamins, sterols, lanolin, and other byeenstituentsproducts which were present in the original oil or One of the objects of the present invention is fat treated or derived therefrom. The glycerine to provide novel and economical methods for the produced is contained in the lower layer of the recovery of valuable by-products, from oils and reaction products.

fatty materials. When employing the latter method to produce Anther object of the invention is to provide a vitamin-containing concentrate, any alcohol methods whereby vitamins, sterols, and other valremaining in the upper layer of material is reuable constituents of fatty materials, may be removed and recovered by distillation at reduced covered without substantial deterioration thereof. temperatures and relatively low pressure, and A further object of the invention is to prothereafter the crude esters, free of alcohol, may

vide novel methods for concentrating vitamins be separated more readily and completely from and other desirable by-products present in oils, the glycerine. The upper ester-containing layer fats, and the like, whereby a high yield of the is then passed to distillation apparatus, preferby-products is assured'and the color of the prodably a vacuum still, where the fatty acid esters ucts obtained is improved. are distilled off, in either a batch operation or 8. These and other objects and features of the continuous operation, leaving the concentrated invention will appear from the following descripsolution of by-products as a, residue.

tion thereof, in which specific examples and meth- In separating the alcohol and alkyl esters, it is ods of procedureare cited for the purpose of inpreferable to employ flash distillation operations dicating the nature of the invention, but Without in order that the material need be maintained at intending to limit the invention thereby. a. high temperature !or only short periods of time. i

.by-products serves apparatus is carried out in an atmosphere of steam, carbon Furthermore. it is found that the exclusion of distillation of the esters and to prevent oxidation and discoloration of the alkyl esters and by-products recovered. The admission of air to the distillation therefore avoided, or distillation is oxygen during the dioxide, nitrogen, or other inert or non-oxidizing gases.

The residue remaining, after separation of the alkyl esters and other constituents of the alcoholysis reaction products by any of the foregoing methods, consists'of a relatively smallvolume of material as compared with the original fatty material treated, and contains unreacted triglycerides and diglycerides as well as the vitamins, sterols, and other valuable by-products. in a high concentration and unimpaired condition. Moreover. when the fatty material treated is of high quality or relatively 'pure, the residue is substantially free of dark-colored oxidation products.

In recovering vitamins from this residue, the material is subjected to distillation and, preferably, is flash distilled at temperatures of from about 165 C. to 300 C. under a pressure not exceeding about mm. of mercury. For example, the distillation can be carried to a temperature of about 200 C. and under a vacuum of not more than about 10 mm. to remove the monoglycerides and remaining high-boiling esters and further concentrate the material. The distillate coming over at higher temperature and lower pressure then can be treated for the recovery of vitamins, sterols, and the like, by extraction by selective solvents, such as aliphatic, cycloaliphatic and aromatic hydrocarbons, chlorinated hydrocarbone, and, preferably, low-boiling hydrocarbons including butane, hexanes and decanes, ,or the like. In the alternative, the extraction and isolation of the vitamins may be effected by chromatographic adsorption, crystallization, or other known methods of purifying or separating chemical materials.

The present invention is adapted for use in treating substantially all animal and vegetable oils or fatty materials which contain vitamins or other by-products, and is applicablespecifically to fatty materials such as menhaden oil, coconut oil, palm oil, olive oil, cottonseed oil, corn oil, tung oil, wool fat, tallow, whale and fish oils, soya bean oil, tall oil, or the like.

In treating such materials, various alcohols may be used for carrying out the alcoholysis reaction, as described more fully in applicant's copending application referred to above. As there pointed out, it is preferable to use short-chain aliphaticalcohols, including aryl substituted aliphatic alcohols, particularly saturated primary alcohols having a boiling point in the presence of excess water lower than 100 C. at atmospheric pressure. and especially the lower aliphatic alcohols having one to about six carbon atoms per molecule, to form fatty acid esters. Specific alcohols satisfactory for use in the reaction include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol. tertiary butyl alcohol, the amyl alcohols, benzyl alcohol, etc. It also is preferable to employ an amount of alcohol at least about twice the calcuated theoretical amount for alcoholysis of the particular glycerides or fatty materials treated, and to maintain substantially anhydrous conditions during the alcoholysis. Better yields of the fatty acid esters are obtained by mixing the reactants in the cold, say at about room tem- 4 heating'the mixture to 9. than when preheating is perature, and then higher temperature, employed.

In selecting an alcoholysis catalyst, an alkaline catafyst is preferred. Among those which have been found suitable for use in the present process are sodium hydroxide, sodium methylate, sodium carbonate, soda ash, and lime. While it is possible to obtain'good yields of the fatty acid esters with very small amounts of catalyst if sufficient time is allowed for the reaction. proportions of about 0.08 mol to about-T30 mol of catalyst per mol of fatty glycerideare preferably employed.

Following this reaction, the unreacted alcohol and glycerine and the alkyl esters are separated from the reaction product to produce a byproduct-containing concentrate from which the vitamins, sterols, lanolin, or the like, may be readily recovered, in the form of light-colored products and in substantially unimpaired condition, by fractionation of the concentrate or by selective adsorption, crystallization, or otherwise.

In order further to indicate the nature of the present invention, the following examples are cited by way of illustration and not by wayof limitation.

Example I Pounds Fraction 1, 1'70-185 C 35.0 Fraction 2, 185210 C 15.0 I Fraction 3, 210-230 C 5.1 Fraction 4, 230-250 C 3.6 Fraction 5, 250-280 C 0.9 Residue 36.4

Fraction 1 is mainly methyl esters. Fractions 2 and 3 are combined and refractionated, yielding 13.1 pounds of material comprising mainly methyl esters together with small amounts of monoand diglycerides and yielding 7.0p0unds of carotene (vitamin A) -containing material which is combined with fraction 4 to make a total of 10.6 pounds of crude, carotene-containing material. This material is further purified by extraction twice with five volumes of equal parts of petroleum ether (as "Skellysolve C) and methanol, the carotene remaining-in the petroleum ether layer. Upon flash distilling off the petroleum ether, there remains 3.6 pounds of crude carotene which is vacuum distilled at 1 .mm. mercur to yield 2.1 pounds of carotene boiling at 220-250 C.

Example II The 10.6 pounds of .crude carot ne-containing material are distilled at 230-260 C. with a stream of steam from a ninety-pound steam main bled purified by chromatographic adsorption on magnesia, using petroleum ether as a solvent, yielding 2.45 pounds of carotene.

Example III Five hundred pounds of menhaden oil are treated with 112 pounds ofmethanol containing 5.64 pounds of caustic soda as a catalyst. The re action is carried out at room temperature.

The resulting reaction product is-flash distilled to remove unreacted alcohol, whereupon the product separates into upper and lower liquid layers. The lower glycerine-containing layer is drawn off, and the upper layer, containing the alkyl esters and vitamin D, is flash distilled at temperatures up to 170 C. under a pressure of from 1 to 3 mm. of mercury. The residue will consist of about 51.0 pounds of a relatively concentrated solution of vitamin D. This residue can be used directly in cattle food and elsewhere where crude vitamincontaining concentrates are employed. However, it may be extracted twice with a mixture of equal parts of benzene and 90% methanol, the vitamin D going into the benzene layer. After flashing off the benzene, 4.8 to 5.4 pounds of still more concentrated oil will remain.

To obtain the substantially pure vitamin, the latter oil concentrate is flash distilled under conditions to collect the fraction boiling at 180- 220 C. at 1 mm. A yield of 3.1 pounds of vitamin D is thus obtained and may be furtherpurifled. if desired, by chromatographic adsorption on aluminum oxide, yielding 1.9 pounds of the final product:

, Example IV One thousand pounds of cottonseed oil are converted to methyl esters and free glycerine by alcoholysis with 241 pounds of methanol containing 8.1 pounds of sodium hydroxide as a catalyst. The excess methanol is flashed off and the esters and glycerine flash distilled without the separation of a glycerlne layer, leaving a distillation residue of about 100 pounds. This residue, in turn, is flash distilled under a pressure of 2 mm. of mercury,'and a fraction collected which comes over at temperatures of from 190 to 200 C. The weight of this fraction will be about 2.4 pounds. This 2.4 pounds of material contain vitamin E (tocopherols), and can be, used as such as an anti-oxidant for soaps, oils, etc., alone or admixed with other preservatives.

If preferred, the concentrate can be further purified to obtain the vitamin E concentrated therein. For this purpose, the concentrate may be subjected to molecular distillation, whereby from 1.30 to 1.55 pounds of substantially pure vitamin E are obtained.

In a further alternative treatment of the 2.4 pounds of concentrate obtained as described above, the material is extracted with equal parts of 90% methanol and petroleum ether, the tocopherol going mainly into the petroleumether phase. Upon flashing off the petroleum ether, 1.8 pounds of tocopherol-containing material are obtained.

If partially hydrogenated cottonseed oil is used as the starting material for the alcoholysis in the foregoing example, esters more valuable for soap making are produced, and the vitamin concentrate is more stable against auto-oxidation.

The concentrate produced may be subjected to chromatographic adsorption in petroleum ether solution on aluminum oxide to eifect further purification of the tocopherols recovered.

ill

Example V Alcoholysis is performed on wool grease which has been preheated and pumped into a heated vacuum chamber to flash off the moisture. After alcoholysis treatment as described above, the pH value of the reaction product is adjusted to 5.0. The reaction products are then flash distilled to obtain the fatty acid esters boiling up to 230 C. under a pressure of 2-3 mm. of mercury, after which the residue containing the cholesterol, cetyi alcohol and lanolin is flash distilled at 1 mm. vacuum to recover and isolate these constituents.

In each of the foregoing examples, the reactions by which the alcoholysis reaction products are obtained are carried out at low temperatures, and the saponification of the vitamin-containing concentrate is avoided. In this way, the conditions under which the concentrate is produced and treated serve to insure the recovery of the byproducts without appreciable deterioration thereof. Furthermore, the volume of the material distilled or extracted in the actual recovery of the vitamins is generally less than 10% of the volume of the oil or fatty material itself.

The present invention also renders it possible to treat a wide variety of fatty materials to recover by-products therefrom in an economical manner. The specific examples cited above are, therefore, only cited as typical of preferred practice in accordance with the present invention, and are not intended to limit the scope of the invention.

This application is a, continuation-in-part of copending application Serial No. 462,370, filed October 17, 1942.

I claim:

1. A process for the recovery of vitamins, ster- I 01s and other valuable constituents from fatty glycerides containing the same which comprises the steps of reacting a fatty glyceride with allphatic monohydrie alcohol having from one to about six carbon atoms per molecule in the pres- 2. The process as set forth in claim 1 in which said fraction is treated with a solvent selective for'said desired valuable constituent, separating the solvent layer and distilling out the solvent.

3. The process as set forth in claim 1 in which said fraction is treated with a c romatographic adsorbent for said valuable constituent, and the adsorbed material recovered therefrom.

4. The process asset forth in claim 1 in which the treatment of said fraction includes fractional distillation at a pressure not exceeding about 1 mm. of mercury.

5. A process for the recovery of a valuable constituent contained in the lower monohydric alcohol esters of fatty ac ds obtained by alcoholysis of a fat containing said constituent which comprises flash distilling the material under such conditions that the esters are largely vaporized and a residue containing pract cally all the valuable constituent is obtained, distilling said residue under such conditions that a major portion of the valuable constituent is vaporized, and condensing said vapor remote from said residue whereby a concentrate of said valuable constituent is obtained.

6. The process as set forth inclaim 5 in which the valuable constituent is carotene and the vathe valuable constituent is vitamin E and the vapor thereof is obtained by flash-distillation within the temperature range of about 190 to 200 C. at 2 mm. of mercury.

WALTER RUSSELL TRENT.

U. s. s. R. 5, 363-4.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,263,550 Andrews Nov. 18, 1941 2,293,551 Kunz -1 Aug. 18, 1942 2,032,006 Cross Feb. 25, 1936 FOREIGN PATENTS Number Country Date 415,088 Great Britain Aug. '17, 1934 OTHER REFERENCES Grandel et al., Application Ser.. No. 414,080, published by the Alien Property Custodian, lMay 11, 1943, 167-81, Box 1. Rosenberg, Bull de Biologie et de Med. Ex.

(Copy in 280-8680.) 

